Thesis Proposal - Université de Toulouse

Submission : 8264
Thesis proposal CSC 2015
Title:
New Shvo-type catalysis for outer sphere hydrogenation catalysis
Thesis supervisor:
Alain IGAU
E-mail address:
[email protected]
PhD School name:
Physics, Chemistry & Material Sciences (SDM)
Research Laboratory:
Laboratoire de Chimie de Coordination (LCC) du CNRS
Laboratory website:
http://www.lcc-toulouse.fr/lcc/?lang=en
Scientific domain:
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Subject short description:
The search for high efficiency catalysts which are involved in chemical reactions
that are economical in terms of atoms, steps required, energy used and waste
produced is a major thrust for today’s industrial plants. One of these “greener”
processes is the transfer hydrogenation reaction. This eco-friendly methodology
permits the reduction of organic polar functions such as ketones and imines to the
corresponding alcohols and amines. The majority of homogeneous hydrogenation
catalysts operate by an inner sphere (IS) mechanism. In the outer sphere (OS)
pathways the substrate does not bind to the metal, H+ and H- are transferred from
the catalyst to the substrate which lead to useful selectivity properties, Noyori’s
asymmetric catalysis, but much more remains to be done in this rapidly developing
field. Ruthenium complexes remain to date the best compromise between price
and reactivity.We recently developed unprecedented tethered etat-5
oxocyclohexadienyl ruthenium(II) Shvo-type catalysts efficient in the conversion of
allylic alcohols to saturated carbonyl compounds (Chem Commun 2013 submitted)
and in the hydration of nitriles to form the corresponding amide (Organometallics
in preparation); both catalysis were performed in water. Our aim is now to test our
complexes in hydrogenation catalysis. Our innovative straightforward pathway
allowed to incorporate and/or coordinate on our bifunctional catalysts stereogenic
centers at different places of their structures in order to test our complexes in
asymmetric catalysis. We also aim to extend our preparative pathway to low cost
metals as iron. Even though inexpensive catalysts have up to now low efficiency;
Morris et al demonstrated the activity of Fe catalysts in OS hydrogenation raction.
The doctorant will learn all the techniques to run experimental reactions under
inert atmosphere. All the spectroscopic intruments to fully characterized the
molecular compounds are available in the laboratory (NMR, IR, Mass
spectrometry, XRD, …). The catalytic tests will be performed with the collaboration
of Dr. M. Urrutigoity at the Ecole Nationale Supérieure des Ingénieurs en Arts
Chimiques Et Technologiques (ENSIACET) in Toulouse. We will use the
computational approach performed by Dr. J. M. Sotiropoulos and K. Miqueu from
Université de Pau et des Pays de l'Adour as a complementary tool to the
experimental approach in order to gain more informations for a better
understanding of the mechanisms that govern the catalytic rections.
Two major publications in the domain of PhD:
Crucial Role of the Amidine Moiety in Methylenamino Phosphine-Type Ligands for
the Synthesis of Tethered η6-Arene-η1-P Ruthenium(II) Complexes: Experimental
and Theoretical Studies
Damien Arquier, Laure Vendier, Karinne Miqueu, Jean-Marc Sotiropoulos,
Stephanie Bastin, and Alain Igau
Organometallics 2009, 28, 4945–4957
Mechanistic analysis of the transition metal-catalyzed hydrogenation of imines and
functionalized enamines
Amandine Fabrello, Alice Bachelier, Martine Urrutigoïty, Philippe Kalck
Coordination Chemistry Reviews 254 (2010) 273–287
M. Kechaou has defended her thesis by september 26th 2013. These innovant
studies will lately appear in Chem Commun and Organometallics.
Keywords: , , , ,
Expected collaboration in China:
First name and family name of the laboratory director:
Azzedine BOUSSEKSOU
Address of the laboratory director:
Laboratoire de Chimie de Coordination du CNRS BP 44099 205 route de Narbonne
31077 Toulouse cedex 4
Signature and stamp of the laboratory director:
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